Granular N-alkyl ammonium acetonitrile compositions

ABSTRACT

Granules are provided that are useful for oxidizing applications when the granules are dissolved in the presence of an active oxygen source. These granules include a salt having the structure of Formula I                    
     wherein A is a saturated ring formed by a plurality of atoms in addition to the N 1  atom, the saturated ring atoms including at least one carbon atom and at least one of O, S, and N atoms, the substituent R 1  bound to the N 1  atom of the Formula I structure including either (a) a C 1-24  alkyl or alkoxylated alkyl where the alkoxy is C 2-4 , (b) a C 4-24  cycloalkyl, (c) a C 7-24  alkaryl, (d) a repeating or nonrepeating alkoxy or alkoxylated alcohol, where the alkoxy unit is C 2-4 , or (e) —CR 2 R 3 C≡N where R 2  and R 3  are each H, a C 1-24  alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit is C 2-4 , the R 2  and R 3  substituents being each H, a C 1-24  alky, cycloalkyl, or alkaryl, or a repeating or nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit is C 2-4 , Z is in the range of 0 to 10, and wherein Y is a counterion. An improved granule is produced when the salt is carried by, coated with, or admixed with a solid particulate such as silica gel, silicic acid, silicate, aluminum oxide, clay, or mixtures thereof.

This application is a continuation in part of Ser. No. 08/758,539, filed Nov. 29, 1996 now U.S. Pat. No. 5,888,419, which is a Continuation-in-Part of Ser. No. 08/475,292, Jun. 7, 1995 now U.S. Pat. No. 5,739,327 entitled “GRANULAR N-ALKYL AMMONIUM ACETONITRILE COMPOUNDS,” inventors Victor M. Casella et al., of common assignment herewith.

FIELD OF THE INVENTION

The present invention generally relates to N-alkyl ammonium acetonitrile compounds useful in applications such as bleaching and cleaning and particularly in the form of granules useful for oxidizing applications when dissolved in the presence of an active oxygen source. The preferred granules will have a high content of the N-alkyl ammonium acetonitrile compounds because of the use of preferred carriers, or supports, such as siliceous solids.

BACKGROUND OF THE INVENTION

Peroxy compounds are effective bleaching agents, and compositions including mono- or di-peroxyacid compounds are useful for industrial or home laundering operations. For example, U.S. Pat. No. 3,996,152, issued Dec. 7, 1976, inventors Edwards et al., discloses bleaching compositions including peroxygen compounds such as diperazelaic acid and diperisophthalic acid.

Peroxyacids (also known as “peracids”) have typically been prepared by the reaction of carboxylic acids with hydrogen peroxide in the presence of sulfuric acid. For example, U.S. Pat. No. 4,337,213, inventors Marynowski et al., issued Jun. 29, 1982, discloses a method for making diperoxyacids in which a high solids throughput may be achieved.

However, granular bleaching products containing peroxyacid compounds tend to lose bleaching activity during storage, due to decomposition of the peroxyacid. The relative instability of peroxyacid can present a problem of storage stability for compositions consisting of or including peroxyacids.

One approach to the problem of reduced bleaching activity of peroxyacid compositions has been to include activators of hydrogen peroxide or an active oxygen source. U.S. Pat. No. 4,283,301, inventor Diehl, issued Aug. 11, 1981, discloses bleaching compositions including peroxygen bleaching compounds, such as sodium perborate monohydrate or sodium perborate tetrahydrate, and activator compounds such as isopropenyl hexanoate and hexanoyl malonic acid diethyl ester.

Other examples of activators include tetraacetyl ethylenediamine (TAED), nonanoyloxy benzene-sulfonate (NOBS), and nonanoylglycolate phenol sulfonate (NOGPS). NOBS and TAED are disclosed, for example, in U.S. Pat. No. 4,417,934, Chung et al., and NOGPS is disclosed, for example, in U.S. Pat. No. 4,778,618, Fong et al., the disclosures of which are incorporated herein by reference.

Thus, U.S. Pat. No. 4,778,618, Fong et al., issued Oct. 18, 1988 provides novel bleaching compositions comprising peracid precursors with the general structure

wherein R is C₁₋₂₀ linear or branched alkyl, alkylethoxylated, cycloalkyl, aryl, substituted aryl; R′ and R″ are independently H, C₁₋₂₀ alkyl, aryl, C₁₋₂₀ alkylaryl, substituted aryl, and N⁺R₃—, wherein R— is C₁₋₃₀ alkyl; and where L is a leaving group which can be displaced in a peroxygen bleaching solution by peroxide anion. U.S. Pat. Nos. 5,182,045, issued Jan. 26, 1993, and 5,391,812, issued Feb. 21, 1995, inventors Rowland et al. are similar, but are polyglycolates of the Fong et al. monoglycolate precursors, or activators.

U.S. Pat. No. 4,915,863, issued Apr. 10, 1990, inventors Aoyagi et al., discloses compounds said to be peracid precursors that have nitrile moieties. U.S. Pat. No. 5,236,616, issued Aug. 17, 1993, inventors Oakes et al., discloses compounds said to be cationic peroxyacid precursors that have nitrile moieties. These nitrile containing activators do not contain a leaving group, such as the Fong et al. leaving groups, but instead include a quaternary ammonium group suggested as activating the nitrile and said, upon reaction or perhydrolysis in the presence of hydrogen peroxide, to generate a peroxyimidic acid as bleaching species. The Aoyagi et al. activators include an aromatic ring, which tends to cause fabric yellowing.

German patent application P4431212.1, published Mar. 7, 1996 describes production of quaternized glycinonitriles in the form of stable aqueous solutions.

New peroxygen activators that provide excellent bleaching and that can be formulated for liquid or solid compositions remain desirable for applications such as laundry and household bleaching and cleaning.

SUMMARY OF THE INVENTION

In one aspect of the present invention, nitrites are provided in substantially solid form having the structure of Formula I

wherein A is a saturated ring formed by five atoms in addition to the N₁ atom, the five saturated ring atoms being four carbon atoms and a heteroatom, the substituent R₁ bound to the N₁ atom of the Formula I structure including either (a) a C₁₋₂₄ alkyl or alkoxylated alkyl where the alkoxy is C₂₋₄, (b) a C₄₋₂₄ cycloalkyl, (c) a C₇₋₂₄ alkaryl, (d) a repeating or nonrepeating alkoxy or alkoxylated alcohol, where the alkoxy unit is C₂₋₄, or (e) —CR₂R₃C≡N where R₂ and R₃ are each H, a C₁₋₂₄ alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit is C₂₋₄.

The Formula I compounds have a quaternary nitrogen atom (N₁), requiring the presence of at least one counterion (Y) to be associated therewith, which is illustrated in Formula I as “Y⁻, ” but as understood can be monovalent, or multivalent. Y includes counterions, or organic and inorganic anions, such as chloride, bromide, nitrate, alkyl sulfate, bisulfate, sulfate, tosylate, and mesylate. Especially preferred are methyl sulfate, sulfate, bisulfate, tosylate, and mixtures thereof. Z will be in the range of 0 to 10. These compounds, or salts, are particularly well suited to granule bleaching and cleaning compositions.

The nitrites with the Formula I structure are particularly useful when formulated as compositions that include a source of active oxygen, and these compositions provide excellent bleaching in alkaline solutions.

Preferred embodiments include lower alkyls substituted at the N₁, e.g. N-methyl morpholinium acetonitrile, N-ethyl morpholinium acetonitrile, N-butyl morpholinium acetonitrile, which are illustrated by Formula II (with “n” preferably being 0 to 24 and where “Y” is one of the above described counterions).

A particularly preferred embodiment is an N-methyl morpholinium acetonitrile salt where “n” of Formula II is 0. Preferred embodiments are in granule form such that the nitrites are stabilized and protected even when formulated or admixed with ether components. Especially preferred are granules produced when the nitrile salts are in liquid or semi-liquid form (that is, as a “melt” or in suspension or solution) and combined with siliceous solids. These particular types of granules have a high content of the nitrile actives.

Compositions including these nitriles are useful, for example, in laundry products, such as bleaching additives, detergents, detergent boosters, detergents with bleach, bleaches, bleaching aids, stain removers, and spot treatment products such as stain removers, prewash and presoak laundry aids. Among the advantages derived from such compositions are improved cleaning, stain removal, spot removal, whitening, and brightening of treated articles.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Arbogast et al., U.S. Pat. No. 5,739,327, entitled “N-Alkyl Ammonium Acetonitrile Bleach Activators,” describes nitriles, typically quaternized, for which a preferred embodiment was N-methyl ammonium acetonitrile methylsulfate, to which this application relates. There are several aspects of the present invention.

One aspect is wherein quaternized nitrites are provided having certain counterions which result in substantially reduced hygroscopicity (with respect to amorphous N-methyl ammonium acetonitrile methylsulfate, or MMAMS). Another aspect is wherein nitriles are provided as granules by being carried, coated, or admixed with a suitable particulate material. These granules have improved stability and/or reduced hygroscopic characteristics with respect to amorphous MMAMS. Yet another aspect of the invention is for an improved process of making novel quaternized nitriles so as to have reduced amounts of undesired by-product.

All these inventive aspects have as a common element certain novel nitriles with the structure generally illustrated by Formula I. The N₁ atom of the Formula I compound is part of a saturated ring, illustrated by “A” in Formula I.

This saturated ring of which N₁ is a part has a plurality of atoms. The saturated ring illustrated by ring “A” in Formula I preferably has at least one hetero atom in the saturated ring in addition to the N₁, more preferably wherein the ring includes an oxygen atom, a sulfur atom, or one or two additional nitrogen atoms.

The at least one nitrogen in the saturated ring (N₁) shown in Formula I is N-acetonitrile substituted and also quaternized. Without being bound by theory, the electron withdrawing nature of the quaternary nitrogen may be increased by being part of a saturated, heterocyclic ring and may also function to improve the hydrophilic character of the oxidant.

A substituent R₁ will be bonded to the N₁ atom of the Formula I structure and additionally a nitrile moiety (—CR₂R₃C≡N) is bonded to the N₁ atom, where R₂ and R₃ are each H, a C₁₋₂₄ alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit is C₂₋₄. The R₁ substituent may be a C₁₋₂₄ alkyl or alkoxylated alkyl where the alkoxy is C₂₋₄, a C₄₋₂₄ cycloalkyl, a C₇₋₂₄ alkaryl, a repeating or nonrepeating alkoxy or alkoxylated alcohol, where the alkoxy unit is C₂₋₄, and illustrative such groups are, for example,

where j=1 to 24. The R₁ substituent may also be another —CR₂R₃C≡N, and again R₂ and R₃ are each H, a C₁₋₂₄ alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit is C₂₋₄, and illustrative such groups are:

where j=1 to 24.

Particularly preferred, saturated rings forming the cyclic configuration A of Formula I contain six atoms including the N₁ atom, but the number of atoms forming the cyclic configuration can range from 3 to 9. When two heteroatoms are present with the cyclic configuration A of Formula I, then a three member ring is unusual; but, for the cyclic configuration B of Formula III shown below, where there may only be N₁ as the sole heteroatom, then three membered rings are very likely.

As already noted, the particularly preferred saturated ring of which N₁ is a part has five atoms in addition to N₁, with at least one hetero atom being in the saturated ring in addition to the N₁, preferably wherein the heteroatom of the ring is an oxygen atom or a sulfur atom, most preferably where the heteroatom is oxygen.

Particularly preferred activator embodiments are illustrated by Formula II (where “Y” and “Z” will be hereinafter described, and “n” is 0 to 24).

Derivatives of the Formulas I and II nitriles include peroxyimidic intermediates that are believed formed from the nitriles in the presence of an active oxygen source. So formed, peroxyimidic derivatives typically would be short-lived intermediates formed in situ when the nitriles of the invention interact with a source of hydrogen peroxide and where the reactive nitrile moiety forms a peroxyimidic acid. However, such peroxyimidic derivatives may also be prepared in situ by analogy to syntheses known in the art.

Counterions

Since the novel nitrile compounds are normally quaternized, they will include at least one counterion (designated as “Y”). Suitable counterions are monovalent or multivalent and include tosylates, lower alkyl tosylate (e.g. methyl tosylate and ethyl tosylate), and mesylates. Further, in U.S. Pat. No. 5,739,327, N-alkyl ammonium acetonitrile compounds are disclosed as typically including a wide variety of counterions such as chloride, bromide, nitrate, alkyl sulfate, and the like, and wherein a preferred embodiment was described therein as N-methyl ammonium acetonitrile methylsulfate.

When one chooses the granule aspect of this invention, then such a wide variety of counterions remain available in choosing which counterion may be desired, including methylsulfate as counterion. This is because most of the granule embodiments protect stability of the nitrile (for example, against humidity during storage). Especially preferred are granules produced when the nitrile salts are in liquid or semi-liquid form and combined with siliceous solids. These particular types of granules have a high content of the nitrile actives. In this preferred form, the preferred nitrile salt is N-alkyl ammonium acetonitrile bisulfate (also referred to as “hydrogen sulfate”), especially N-methyl ammonium acetonitrile bisulfate, and the preferred siliceous solid, or support, is silica, silicic acid, alkali metal silicate, or a combination thereof. These types of granules perform especially well in situations where a higher level of oxidation is needed, such as for especially soiled soft and hard surfaces, or where a white or non-colored fabric is sought to be cleaned.

Thus, particularly preferred embodiments are where the counterions are either sulfate, bisulfate, or mixtures thereof. Such a sulfate or bisulfate salt (or mixtures thereof) may be produced from heated and acidified N-methyl morpholinium acetonitrile methylsulfate, or MMAMS (wherein the counterion before the conversion to bisulfate or sulfate is methylsulfate). These two particularly preferred salts are illustrated by Formula IIIA and IIIB. A third particularly preferred salt, N-methyl morpholinium acetonitrile tosylate (“MMATS”), is illustrated by Formula IIIC.

The MMABS, MMAS, and MMATS embodiments are particularly useful where one wishes a substantially solid composition to have reduced hygroscopicity with respect to MMAMS. Although the MMABS, MMAS, and MMATS embodiments may also be in granule form, they need not be, and are usable in crystalline or amorphous forms.

The sulfate and bisulfate counterions are in equilibrium with one another in solution, and the predominant species is dependent on the solution pH. Above pH 2, the sulfate group predominates, while below pH 2 the bisulfate form predominates. Thus, the particular form desired may be obtained by controlling the solution pH, although a mixture is obtained at an intermediate pH.

In one preferred embodiment, the granules in which the nitrile salt is bisulfate has been crystallized, the crystals redissolved, and the solution (thus having impurities removed) is granulated. In yet another preferred embodiment, the bisulfate salt, after having undergone conversion from the methylsulfate salt, with impurities and by-products also removed, is maintained in the liquid or semi-liquid phase, heated to drive off, or otherwise remove, excess water, and then promptly combined with the siliceous support, resulting in solid granules of high nitrile actives content. In such a preferred embodiment, the production of granules can thus be made continuously, resulting in an economically very favorable production. While this continuous conversion is readily preferred, a batch or semi-continuous process is also preferred and is part of the invention.

Nitrile Water Content

The novel nitriles may exist either as anhydrous salts (essentially free of water) or as stable hydrates having discrete amounts of water of hydration. Thus, in Formulas I and II, Z is in the range of 0 to 10, preferably 0 to 6, and most preferably 0 to 1. This “Z” may be viewed as an average number of moles of hydration. Because there may be mixtures of the Formulas I and II compounds with integer numbers of moles of hydration, the actual value for Z may be a non-integer value. The value for Z may be reduced when one converts a crystalline, amorphous or liquid form of nitrile into a granulated form.

Physical Form of Nitriles

Amorphous forms of the Formulas I and II nitrites may be obtained by rapid evaporation or precipitation from solutions (such as in spray drying, column drying, and the like). Alternatively, crystalline salts may be obtained by crystallization or careful evaporation, which crystalline forms tend to be less hygroscopic than amorphous forms. This reduced hygroscopicity of the crystalline salts is believed, without being bound to theory, due to the tight packing of the molecules within the crystal that prevent bulk water penetration and the reduced total surface area of a crystalline solid compared to an amorphous form of the same solid. Granule embodiments may also be prepared from the nitrites in either the crystallized, amorphous or liquid forms. As stated above, it has been found advantageous to take the liquid form of the nitrile salts and to combine them, promptly or immediately after converting from the methyl sulfate to the bisulfate, with the siliceous supports.

Surprising Properties of the Nitrile Granules

Granule embodiments have the advantage of being shelf stable (that is, remaining capable of flowing without clumping, caking, or otherwise agglomerating) and maintaining bleaching effectiveness until use, even when the granules are formulated or admixed with other components, such as sources of alkalinity and of active oxygen. Further, granule protection permits use of a lower amount of nitrites in granule formulations used in bleaching and laundering preparations which reduces possible dye damage. Dye damage may be caused upon dissolution of the formulations when inadvertently placed in direct contact with textiles having particularly sensitive dyes. However, when optimal bleaching performance is desired, with lesser concern about possible dye damage, particularly when the nitriles are formulated as granules in laundry bleaches or bleach detergents specified for use on colorless or white fabrics, it is especially desirable to load a high level of the nitrile active onto the solid support. In this latter instance, it has been found that it is most preferred to take the liquid form of the nitrile salts and to combine them, promptly or immediately after converting from the methyl sulfate to the bisulfate, with the siliceous supports, to form especially stable, high actives content granules.

Bleaching and Cleaning Compositions

Bleaching and cleaning compositions of the invention include the Formula I nitrile salts as activator, together with a source of active oxygen.

The peroxide or active oxygen source for compositions of the invention may be selected from the alkaline earth metal salts of percarbonate, perborate, persilicate and hydrogen peroxide adducts and hydrogen peroxide. Most preferred are sodium percarbonate, sodium perborate mono- and tetrahydrate, and hydrogen peroxide. Other peroxygen sources may be possible, such as monopersulfates and monoperphosphates, or their equivalent aqueous forms, such as monopersulfuric acid, known in the trade as Caro's acid or Caroate, a product of BASF AG, Germany.

The range of peroxide to activator is preferably determined as a molar ratio of peroxide to activator. Thus, the range of peroxide to each activator is a molar ratio of from about 0.1:1 to 100:1, more preferably about 1:1 to 10:1 and most preferably about 2:1 to 8:1. This peracid activator/peroxide composition should provide about 0.5 to 100 ppm A.O., more preferably about 1 to 50 ppm peracid A.O. (active oxygen), and most preferably about 1 to 20 ppm peracid A.O., in aqueous media for typical laundry applications. Formulations intended for hard surface cleaning will more typically have peracid activator/peroxide providing from about 0.5 to 1,000 ppm A.O., more preferably about 1 to 500 ppm peracid A.O., and most preferably about 1 to 200 ppm peracid A.O.

Compositions of the invention have been found to provide superior bleaching (cleaning and stain removal) benefits on common laundry stains.

Granular Embodiments and Delivery Systems

The substantially solid salt activators can be directly used in a crystalline or amorphous form, for example by incorporating into a solid matrix in solid detergent bleaches. As will be hereinafter more fully described, preparation of the nitriles in bisulfate or sulfate form will typically be by converting from another counterion (e.g. methylsulfate). The conversion may be complete or partial. Thus, a Formula I or II salt composition may include from about 1 wt. % to about 99 wt. % of another compound related to the Formula I compound, but differing therefrom in counterion. The degree of conversion to bisulfate or sulfate will be directly related to the amount of hygroscopicity reduction of such a salt composition.

Whether converted to bisulfate or sulfate or not, incorporation of the novel nitrile salts into dry, or granulated, formulations can be achieved through several different embodiments. Granulated formulations hold several advantages over liquid formations, such as for example, reduced shipping costs. Other advantages are an increased stability of the nitrile activator against moisture, alkalinity (e.g. carbonate), against premature activation, and reduction in possible dye damage.

Typically, the precursor composition before granulation is of sprayable consistency, that is to say, in the form of a melt, suspension, or solution. One suitable process for granulation may be performed in a fluid bed or rotary drum agglomerator, such as is described by Iliff et al., U.S. Pat. No. 5,605,883, incorporated herein by reference.

In the granular embodiments the nitrile salts can be carried by, coated with or admixed with a solid particulate, such as an inert, porous material. These granules can further have a coating that is sufficient to delay dissolution in aqueous solution. For example, appropriate such coatings include surfactants, waxes, polymers, or melts thereof, and dusting or flow agents such as silicas and silicates. The coatings can encapsulate the nitrile-containing core.

Granules preferably have an average particle size of from about 3 nm to about 2 mm. For example, activators of the invention can be dispersed onto a solid or granulated carrier such as silica gel, silicic acid, silicate, aluminum oxide, kaolin, aluminum silicate, mixtures or other carriers such as clay, organic polymers including starch and ion exchange material. Additional solids useful for carriers include alkali metal and alkaline earth salts of carbonate, bicarbonate, sesquicarbonate, phosphate, chloride, sulfate, bisulfate, and borate. Especially preferred herein are the siliceous solids, namely, silica, alkali metal (sodium, lithium, potassium, or mixtures thereof) silicates, silicic acid and mixtures thereof. Additionally, alkali metal (preferably, sodium) sulfates can be present, in place of, or in addition to, the siliceous material.

A high internal surface area of the carrier materials is preferred for such a granular embodiment. The total surface area preferably lies in the range from 10 to 500 m²/g or, especially, 100 to 460 m²/g or, especially, 250 to 450 m²/g.

Although most conventional types of chemically inert, porous materials can be used as carrier materials, silicic acids, silicates, precipitated silicas, aluminum oxides, various varieties of clays or aluminum silicates or mixtures thereof are preferred.

Silica gels (silica gels, silicic acid gels) are colloidal, formed or unformed silicic acids of elastic to solid consistency with a loose to compact pore structure and a high adsorption capacity. Silica gel surfaces usually exhibit acidic properties. Silica gel is usually manufactured from water-glass by reaction with mineral acids. Precipitated silicas are powders obtained by coagulation of silica particles from an aqueous medium under the influence of coagulants.

Among the silicic acids, thermally generated silicic acids, i.e. highly dispersed “pyrogenic” SiO₂ qualities (e.g. the Aerosils® or Cab-o-Sils®) that are usually prepared by flame hydrolysis of SiCl₄ can be used especially advantageously in addition to silicic acids that are obtained in accordance with the wet process. In a specially preferred form of embodiment of the present invention, use is made of silicic acid with an average (agglomerate) particle size of 100 nm or 30 mm or, especially, 100 μm to 1.5 mm and a SiO₂ content of 95 to 100% by weight or, preferably, 98 to 100% by weight. In addition, precipitated silicone, such as SIPERNAT® silica material can be used advantageously.

Aluminum oxides occur in nature in, for example, the form of argillaceous earth or as corundum. In this regard, the aluminum oxide is present in the α-modification. Industrially, α-Al₂O₃ is obtained from bauxite using the Bayer process. Suitable “active” aluminum oxides with a high specific surface area are prepared in the form of adsorbents, via precipitation procedures, from aluminum salt solutions or via the calcination of α-aluminum hydroxide.

Clays are naturally occurring crystalline and amorphous hydrated silicates of aluminum, iron, magnesium, calcium, potassium, and sodium. These clays may also contain amounts of aluminum oxides and silica. Useful clays may include kaolins, serpentines, talcs, pyrophyllites, attapulgites, sepiolites, montmorillonites, and bauxitic clays. These clays may undergo various processes before use. For example, clays may be air-floated, water-washed, calcined, delaminated, acid activated, or treated with dispersants.

One preferred process for providing an aluminum silicate carrier particle is disclosed by Iliff et al., U.S. Pat. No. 5,605,883, noted above, which process can also be used for providing a carrier for a pigment or other colorant. Aluminum silicates are compounds with different proportions of Al₂O₃ and SiO₂. Aluminum silicate minerals in which Al occupies lattice positions in the crystal lattice in the place of Si are the aluminosilicates (e.g. the various varieties of ultramarine, zeolite, and feldspar). Freshly precipitated aluminum silicates are finely dispersed and have a large surface area and a high adsorption capacity. Among usefull aluminosilicates are synthetic zeolites commonly used as detergent builders.

Especially preferred is, however, when the bisulfate salt, after having undergone conversion from the methylsulfate salt, with impurities and by-products also removed, is maintained in the liquid or semi-liquid phase, heated to drive off, or otherwise remove, excess water, and then promptly combined with the siliceous support, resulting in solid granules of high nitrile actives content. In such a preferred embodiment, the production of granules can thus be made continuously, resulting in an economically very favorable production. While this continuous conversion is readily preferred, a batch or semi-continuous process is also preferred and is part of the invention.

The ratio of nitrile salt and carrier materials in a solid composition in accordance with the invention can vary within certain limits, depending on the method of manufacturing the solid composition and the properties of the carrier, and the final end use. A preferred ratio is 10 to 95 parts by weight of the nitrile to 5 to 90 parts by weight of the carrier, especially 10 to 70 parts of weight of the nitrile to 10 to 70 parts by weight of the carrier. A ratio of 50 to 90 parts by weight of Formula I to 10 to 50 parts by weight of carrier is especially preferred where the desire is to maximize the concentration of active Formula I. A ratio of 50 to 10 parts by weight of Formula I to 10 to 90 parts by weight of carrier is especially preferred where the desire is to disperse the active Formula I, for instance to reduce localized bleaching. The indicated parts by weight are based on the anhydrous solid. For example, granules of the invention may include one surfactant or a mixture of surfactants so as to constitute an amount preferably of about 0.5 to about 50 parts by weight.

Improved Preparation of High Nitrile Actives Content Granules

The following description is for an improved process for preparing the inventive granules.

The process has two major objectives:

(1) removal of water and solvent (generally, methanol) in an evaporative step; and

(2) solidification of the so-called “melt” (the “melt” is a suspension of MMA-Bisulfate obtained in previous step) with or without carriers and process aids.

In the inventive process, the aqueous MMA-Methyl Sulfate solution will be subjected to a continuous evaporation process. Evaporation can take place in a batch type process, e.g. in a vessel or other defined volume reactor. Continuous evaporation is a further preferred process however, such as, e.g.s. in a Sambay, in a thin film contact dryer, falling film evaporator or in a shell and tube heat exchanger. There are many other types of continuous reactors known to those skilled in the art.

Evaporation can occur under atmospheric pressure, at greater than atmospheric pressure and under vacuum. Atmospheric pressure and slight vacuum may be preferred, because volatile byproducts can be easily removed under these conditions. Batch processes, for example, in a reactor, can also be advantageously used.

Depending on the pressure, which can vary from about 100 mbar to 2 bar, the evaporation can take place at a temperature range of 80° C.-250° C. In an especially preferred pressure range the favorable temperatures are between 100° C. and 160° C., at a pressure of about 250 to 900 mbar, because the water and any solvents (e.g., methanol) are optimally stripped off, while the breakdown of MMA Bisulfate to less desirable by-products may be avoided or mitigated. Applicants believe, but are not bound by theory, that if the MMA-Bisulfate is allowed to reside at a relatively high temperature for a long period of time, a hydrolysis reaction may occur, resulting in the conversion of the nitrile to an amide. The ultimate end result is that the desired active, MMA-Bisulfate, would thus be reduced.

The required residence time in the continuous process depends on the applied pressure and temperature, and can extend from few minutes to several hours. Under the above mentioned conditions the residence times are most favorable between 5 and 15 minutes. Longer residence time may cause product degradation, as discussed above. Residence time distribution should be also narrow, in order to avoid the formation of byproducts and decomposition products.

The output of the evaporation process will be a melt of the MMA-Bisulfate as well as volatile vapors (mostly water and solvents, e.g., methanol). The energy input to the process mentioned by the invention can be significantly reduced by utilizing the latent heat of the vapors for preheating the incoming solution. For this purpose various heat exchangers, e.g.s. plate and frame and shell and tube heat exchangers, could be used.

The melt obtained by this process has a water content between 0% and 30%, and the MMA-Bisulfate to MMA-Methylsulfate ratio is at least 50%, but preferably, greater. This melt is then subjected to the second process step, which is the solidification with or without the addition of carriers and process aids, and can be processed differently in the subsequent manufacturing steps.

Before the solidification the melt can be mixed with the carriers. The carriers could be soluble or insoluble in water, depending on the application. Examples for carriers: sodium sulfate, the preferred siliceous materials (such as silica, silicic acid, silicate, or mixtures thereof). Beside carriers, functional additives as surfactants can be introduced to the melt as well. Blending of these ingredients can be done in a separate equipment, e.g. in an agitated vessel, or in a continuous mixer. The mixture then can be solidified by contact cooling (cooling roller, cooled conveyor or cooling mixer) or by convective cooling (e.g. in a prill tower or spray tower). It is also possible to carry out mixing and solidification in the same equipment, e.g. in an extruder, in a mixer with kneading action, or in a mixer-cooler.

The cooling process can take place under vacuum, under atmospheric pressure and under greater than atmospheric pressure. Preferred pressure is atmospheric or slight vacuum by aspiration.

The temperatures of the cooling can range from the solidification temperature of the mixture to negative temperatures e.g. by the application of liquid nitrogen. Preferred temperature range is between −50° C. and +30° C., most preferably between about −20° C. and +20° C.

The required residence time for the solidification depends on the crystallization properties of the mixture, and it can take from a few minutes up to a couple of hours or so. In most cases intensive mixing action (e.g. in an extruder or in a kneading type mixer) may be preferred, as it can reduce the crystallization time significantly, if such step is desired.

After solidification the particle size distribution of the MMA-Bisulfate or MMA-Bisulfate along with carriers and/or process aids, may not be as desired, as the particle size may be too large, too uneven, or too fine. Thus, optimal particle size distribution can be achieved by using a classification and milling step in equipment widely used and well known in solids processing. The general particle size ranges from about 100 to 5,000μ, preferably from 300 to 2,000μ.

This inventive process has a number of advantages. First, the conversion takes place with diminished by-products and a reduction of less desired products of the reaction. Use of a continuous conversion results in a high yield. The continuous process is also advantageous in terms of safety as it lessens stops and starts in the plant. Because it is possible to have heat recovery in this system, an energetically favorable process results. A wide variety of different supports and adjuncts can be used in the granulation process. Moreover, control of particle size distribution in the granulation process is quite practicable.

Surfactants of Delivery Systems

As earlier mentioned, compositions of the invention frequently desirably contain varying amounts of surfactants, which may act both as a cleaning active agent as well as also to help disperse sparingly soluble materials in liquid phase when the compositions are put to use.

Surfactants with which the activators and active oxygen compositions may be combined or admixed include linear ethoxylated alcohols, such as those sold by Shell Chemical Company under the brand name Neodol. Other suitable nonionic surfactants can include other linear ethoxylated alcohols with an average length of 6 to 16 carbon atoms and averaging about 2 to 20 moles of ethylene oxide per mole of alcohol; linear and branched, primary and secondary ethoxylated, propoxylated alcohols with an average length of about 6 to 16 carbon atoms and averaging 0-10 moles of ethylene oxide and about 1 to 10 moles of propylene oxide per mole of alcohol; linear and branched alkylphenoxy (polyethoxy) alcohols, otherwise known as ethoxylated alkylphenols, with an average chain length of 3 to 16 carbon atoms and averaging 1.5 to 30 moles of ethylene oxide per mole of alcohol; and mixtures thereof.

Further suitable nonionic surfactants may include polyoxyethylene carboxylic acid esters, fatty acid glycerol esters, fatty acid and ethoxylated fatty acid alkanolamides, certain block copolymers of propylene oxide and ethylene oxide, and block polymers or propylene oxide and ethylene oxide with propoxylated ethylene diamine. Also included are such semi-polar nonionic surfactants like amine oxides, phosphine oxides, sulfoxides and their ethoxylated derivatives.

Anionic surfactants may also be suitable. Examples of such anionic surfactants may include the ammonium, substituted ammonium (e.g., mono-, di-, and triethanolammonium), alkali metal and alkaline earth metal salts of C₆-C₂₀ fatty acids and rosin acids, linear and branched alkyl benzene sulfonates, alkylethoxylated ether sulfates, alkylethoxylated or propoxylated ether sulfates, alkyl sulfates, alkyl ether sulfates, alkane sulfonates, alpha olefin sulfonates, hydroxyalkane sulfonates, fatty acid monoglyceride sulfates, alkyl glyceryl ether sulfates, acyl sarcosinates and acyl N-methyltaurides.

Suitable cationic surfactants may include the quaternary ammonium compounds in which typically one of the groups linked to the nitrogen atom is a C₁₂-C₁₈ alkyl group and the other three groups are short chained alkyl groups which may bear inert substituents such as phenyl groups.

Suitable amphoteric and zwitterionic surfactants containing an anionic water-solubilizing group, a cationic group or a hydrophobic organic group include amino carboxylic acids and their salts, amino dicarboxylic acids and their salts, alkyl-betaines, alkyl aminopropylbetaines, sulfobetaines, alkyl imidazolinium derivatives, certain quaternary ammonium compounds, certain quaternary phosphonium compounds and certain tertiary sulfonium compounds.

Other common detergent adjuncts may be added if a bleach or detergent bleach product is desired. Table 1 illustrates dry bleaching composition embodiments incorporating the Formula I salts.

TABLE 1 COMPONENT COMPONENT RANGES (Wt. %) Surfactant: Linear alkyl benzene sulfonate  0-15 (LAS) Alkyl Sulfate (AS) Alcohol ethoxy sulfate (AEOS)  0-15 Alcohol ethoxylate (AE)  0-15 Builder: Sodium carbonate 20-70 Zeolite  0-50 Polyacrylate polymer 0-5 Sodium silicate 0-8 Filler: Sodium chloride  0-30 Sodium sulfate  0-30 Water 0-5 Bleaching System: Sodium perborate monohydrate  4-40 MMA¹ activator  1-10 Other: Enzyme(s)² 0-3 Brightener 0-2 Dye/Pigment as needed Perfume as needed ¹Inventive nitrile, preferably MMAMS, MMAS, MMABS, or MMATS. ²Examples include but are not limited to protease, amylase, lipase, cellulase (alone or in combinations)

Sources of Acid/Alkali

Compositions of the invention, when combined with a source of active oxygen, preferably function for bleaching best at an alkaline pH, but are shelf-stabilized best at an acidic pH, particularly a pH of from 0-5, more preferably 0-2, most preferably 0-1. Thus, compositions of the invention preferably include a source of protons as an “acid sink.” This can be achieved, for example, by adding acid, preferably at levels from about 0-50 wt. % of final solid weight to liquid containing the nitrites prior to any further granulation processing (mixing or drying). Preferred acids include citric acid, sulfuric acid, alkali metal (sodium, potassium, lithium or mixtures) hydrogen sulfate, succinic acid, hydrochloric acid, sulfurous acid, aryl sulfonic acids and alkyl aryl sulfonic acids, as well as polyacrylic acid, maleic acid, nitric acid, and sulfamic acid.

When the composition is ready for use, it is especially advantageous to have an amount of alkaline buffer present sufficient to maintain a pH greater than about 8, more preferably in the range of about 8.5 to about 10.5 for most effective bleaching, when the granules are dissolved or dispersed into an aqueous wash system. If used as a hard surface cleaner, on the other hand, it may be useful to co-dispense the alkaline buffer in a separate, preferably liquid, composition. These alkaline buffers include, but are not limited to, alkali metal hydroxides (sodium, lithium, potassium), ammonium hydroxide, alkali metal and ammonium carbonates, alkali metal and ammonium carbamates, alkali metal and ammonium polyacrylates, alkali metal and ammonium succinates, alkali metal and ammonium maleates and additional conjugate bases of weak organic acids, such as those mentioned hereinabove. Further, organic bases are included, such as, without limitation, ethanolamine, diethanolamine, triethanolamine, hydroxy amine, methylamine, dimethylamine, and trimethylamine.

Additional Functional/Aesthetic Adjuncts

Other adjuncts (useful in cleaning and laundering applications) are optionally included in the inventive compositions. Dyes include anthraquinone and similar blue dyes. Pigments may also be used, and can have a bluing effect by depositing on fabrics washed with a detergent bleach containing UMB. Monastral colorants are also possible for inclusion. Brighteners or whiteners, such as stilbene, styrene and styrylnaphthalene brighteners (fluorescent whitening agents), may be included. Fragrances used for aesthetic purposes are commercially available from Norda, International Flavors and Fragrances, and Givaudon. Stabilizers include hydrated salts, such as magnesium sulfate, and boric acid.

In some of the compositions herein, adjuvants include (and are especially preferred) a chelating agent or sequestrant, and preferably a non-phosphate containing sesquesterant, and most preferably, an aminopolyphosphonate. These chelating agents assist in maintaining the solution stability of the salt activators and active oxygen source in order to achieve optimum performance. In this manner, they are acting to chelate heavy metal ions, which cause catalyzed decomposition of the active oxygen source and of the (believed) in situ formed peroxyimidic acids, although this is a non-binding theory of their action and not limiting.

The chelating agent is selected from a number of known agents which are effective at chelating heavy metal ions. The chelating agent should be resistant to hydrolysis and rapid oxidation by oxidants. Preferably, it should have an acid dissociation constant (pKa) of about 1-9, indicating that it dissociates at low pH's to enhance binding to metal cations. Acceptable amounts of the (optional) chelating agent range from 0-1,000, more preferably 5-500, most preferably 10-100 ppm chelating agent, in the wash liquor.

The most preferred chelating agent is an aminopolyphosphonate, which is commercially available under the trademark Dequest from Monsanto Company. Examples thereof are Dequest 2000, 2041, and 2060. (See also Bossu U.S. Pat. No. 4,473,507, column 12, line 63 through column 13, line 22, incorporated herein by reference.) A polyphosphonate, such as Dequest 2010, is also suitable for use.

Other preferred non-phosphate containing chelating agents, such as ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) may also be suitable for use. Still other new, preferred chelating agents are new propylenediaminetetraacetates, such as Hampshire 1,3 PDTA, from W. R. Grace, and Chel DTPA 100#F, from Ciba Creigy A.G. Mixtures of the foregoing may be suitable.

Additional desirable adjuncts are enzymes (although it may be preferred to also include an enzyme stabilizer). Proteases are one especially preferred class of enzymes. They are preferably selected from alkaline proteases. The term “alkaline,” refers to the pH at which the enzymes' activity is optimal. Alkaline proteases are available from a wide variety of sources, and are typically produced from various microorganism (e.g., Bacillus subtilisis). Typical examples of alkaline proteases include Maxatase and Maxacal from International BioSynthetics, Alcalase, Savinase, and Esperase, all available from Novo Industri A/S. See also Stanislowski et al., U.S. Pat. No. 4,511,490, incorporated herein by reference. Further suitable enzymes are amylases, which are carbohydrate-hydrolyzing enzymes. It is also preferred to include mixtures of amylases and proteases. Suitable amylases include Rapidase, from Societe Rapidase, Milezyme from Miles Laboratory, and Maxamyl from International BioSynthetics.

Still other suitable enzymes are cellulases, such as those described in Tai, U.S. Pat. No. 4,479,881, Murata et al., U.S. Pat. No. 4,443,355, Barbesgaard et al., U.S. Pat. No. 4,435,307, and Ohya et al., U.S. Pat. No. 3,983,082, incorporated herein by reference.

Yet other suitable enzymes are lipases, such as those described in Silver, U.S. Pat. No. 3,950,277, and Thom et al., U.S. Pat. No. 4,707,291, incorporated herein by reference.

The hydrolytic enzyme should be present in an amount of about 0.01-5%, more preferably about 0.01-3%, and most preferably about 0.1-2% by weight of the composition. Mixtures of any of the foregoing hydrolases are desirable, especially protease/amylase blends.

Anti-redeposition agents, such as carboxy methylcellulose, are potentially desirable. Foam boosters, such as appropriate anionic surfactants, may be appropriate for inclusion herein. Also, in the case of excess foaming resulting from the use of certain surfactants, anti-foaming agents, such as alkylated polysiloxanes, e.g. dimethylpolysiloxane, would be desirable.

Preferred Granule Size, Density and Shape

Granule particle sizes can range from about 100 μm to about 1200 μm, more preferably 150-850 μm. Granule density will normally range from about 0.5 g/c³ to about 1.0 g/c³, more preferably 0.65 g/c³ to about 0.80 g/c³. A wide variety of granule shapes may be used, including spheres, hearts, moons, stars, clovers, cylindrical sections, and cubic sections.

Applications

Compositions of the invention are useful as or in laundry products, such as bleaching additives, detergents, detergent boosters, detergents with bleach, bleaches, bleaching aids, and stain removers. Among the advantages derived from compositions of the invention are improved cleaning, stain removal, spot removal, whitening, and brightening of treated articles.

Other product applications include household cleaning products, such as hard surface cleaners to be wetted with or dissolved in water prior to use. Exemplary surface cleaners are tile and grout cleaners, bathroom (floor, toilet, and counter) and kitchen (floor, sink, and counter) cleaners. Additionally, kitchen products such as dishwasher detergents with bleach or bleach cleaning and scrubbing pads are contemplated. Among the benefits derived from use of the inventive compositions in such applications are improved stain and spot removal and general cleaning of the treated surfaces to remove food, rust, grime, mildew, mold, and other typical stains found on such surfaces.

Additionally, non-household product applications are contemplated where an effective level of active oxygen generated in situ to treat water is useful. Illustrative of such applications are pool and spa additives, as well as cleaners to remove stains on outdoor concrete, stucco, siding, wood and plastic surfaces.

Preparation of the Nitriles

In general, N-quaternary acetonitrile compounds may be readily prepared from N-acetonitrile precursors by employing selected alkyl halides and using well-known synthetic approaches, such as are described by Menschutkin, Z. Physik. Chem., 5, 589 (1890), and Z. Physik Chem., 6, 41 (1890); Abraham, Progr. Phys. Org. Chem., 11, 1 (1974); Arnett, J. Am. Chem. Soc., 102, 5892 (1980); German application DE 05 44 312 212. One may also note the teachings of published PCT Application WO 98/23601, published Jun. 4, 1998 and entitled “PROCESS FOR PREPARING N-ALKYL AMMONIUM ACETONITRILE COMPOUNDS.” All these are incorporated by reference.

Compounds having the Formula I structure have a saturated ring formed by a plurality of atoms, broadly ranging from 3 to 9, although preferably containing 6 atoms including the N₁ atom. Preparation of these compounds will most conveniently start with a compound already having the formed ring. For example, a number of preparations of inventive nitriles hereinafter described will begin with morpholine (see, e.g., the Formula II structure). An example of three membered rings is aziridine, e.g., N-methylacetonilrile aziridinium; as an example of four membered rings there is azetidine, e.g., N-ethyl-acetonitrile azetidinium; as an example of five membered rings there is pyrrolidine, e.g., N-butylacetonitrile pyrrolidinium; as an example of six membered rings, in addition to morpholine, there is piperidine, e.g., N-methylacetonitrile piperidinium; as an example of seven membered rings there is homopiperidinium; as an example of eight membered rings there is tropane, e.g., N-methylacetonitrile-8-azabicyclo[3.2.1]octane; and, as an example of nine membered rings there is octahydroindole, e.g., N-methylacetonitrile octahydroindolinium.

More particularly, in the preferred method of preparation a suitable amine is reacted with a monoaldehyde or a dialdehyde and with HCN or an alkali metal cyanide in an aqueous medium (Step A) followed by subsequent quaternization (Step B) with an alkylating agent. In Step A, the reaction is preferably either in the pH range from 8 through 14, and the pH value is maintained at not less than 2 in Step B.

Thus, an amine with the formula

is reacted as Step A with a monoaldehyde or a dialdehyde R⁶—CHO or OHC—R⁵—CHO, whereby R⁵ is a chemical bond or a C₁ to C₆ alkylene bridge or an oxyethylene bridge, and R⁶ stands for H or C₁ to C₂₀ alkyl, and with hydrogen cyanide or an alkali metal cyanide in an aqueous medium. Step B is quaternization with an alkylating agent R¹—X in an aqueous medium without isolating the intermediate product from Step A. Preferred alkylating agents are dimethylsulfate, diethyl sulfate, a methyl halide, an ethyl halide, dimethyl carbonate, diethyl carbonate, methyl tosylate, ethyl tosylate, methyl mesylate, ethyl mesylate, or a benzyl halide.

In Step A, cyanohydrins, e.g., formaldehyde cyanohydrin, can be formed as by-products from the aldehyde, that is used, and hydrogen cyanide. These cyanohydrins do not react further with the alkylating agent in Step B so that renewed breaking down of the cyanohydrins into aldehyde and hydrogen cyanide in the final product is possible.

Without the procedure in accordance with the invention, Step B usually proceeds in such a way that, as a result of hydrolysis of the added alkylating agent the pH value of the reaction mixture drifts off from the alkaline or neutral region into the strongly acidic region with increasing reaction time. The protonation of the amine nitrogen atom of the glycinonitrile, that has not yet been quaternized, sets in-in competition with alkylation—starting from a certain pH value so that, at the end of the addition of the alkylating agent, no further reaction of the glycinonitrile takes place. Non-quaternized glycinonitrile in the final product can also represent an undesired source of hydrogen cyanide.

Step A generates especially good results if a pH range of 9 through 13 or, especially, 10 through 12, is utilized. In this pH range, the cyanohydrin that is formed is present in an equilibrium with the aldehyde and the hydrogen cyanide so that the re-formed adducts can react to completion with the amine to give glycinonitrile.

If one also uses an excess of amine that amounts to about 2 through 20 mole % or, especially, about 3 through 10 mole % or, most particularly of all, about 4 through 7 mole %, based on the quantity of the hydrogen cyanide or alkali metal cyanide that is used, then one achieves even more extensive suppression of hydrogen cyanide and ancillary components, that liberate hydrogen cyanide, in the final product.

Step B generates especially good results if the pH values are not reduced below 2.5 and, especially, not below 3. An optimum pH range for the quaternization of Step B is 2.5 through 5 or, especially, 3 through 4.

Use is also made of an excess of alkylating agent that amounts to 10 to 40 mole % or, especially, 15 to 25 mole % based on the quantity of amine that is used in Step A, then one achieves still more extensive suppression of the hydrogen cyanide and the subsidiary components, that liberate hydrogen cyanide, in the final product.

Once the nitriles are prepared in quaternized form, formation of the preferred bisulfate or sulfate form preferably is by heating an alkyl sulfate form, in an acid aqueous solution. For example, a suitable elevated temperature is about 40° C. to about 150° C., more preferably about 70° C. to about 110° C. The acid aqueous solution may have a pH in the range of about −1 to 6, more preferably from about 0 to 3, with the heating being for a period of about 1 to 50 hours.

Aspects of the invention will now be illustrated by the following examples. It will be understood that these examples are intended to illustrate, and not to limit, the invention.

EXAMPLE 1

527.2 g (6.05 moles) of morpholine were introduced into the reaction vessel and cooled to 10° C. Within a period of one hour, 600 g (6.0 moles) of formaldehyde (30% by weight) were then metered in. The addition of 161.6 g (5.94 moles) of hydrogen cyanide (99.25% by weight) started half an hour after the start of the addition of formaldehyde. The time of addition amounted to 1 hour. During the addition, the temperature was allowed to rise to 35° C. and stirring then took place for a further hour at 35° C. Cooling to 30° C. then took place and 927.8 g (7.35 moles) of dimethylsulfate (DMS) were added within 2 hours at 30° C. During the DMS addition, the pH value fell into the acidic region starting from 8. At pH 3.5, the pH-regulated addition of aqueous caustic soda (25% by weight) was counter-controlled so that the pH remained constant at 3.5 during the remaining addition time and the following post-reaction time of 3 hour at 30° C. The mixture was then heated to 50° C. and the pH value was allowed to fall in this connection. After 1 hour at 50° C., the excess DMS was completely destroyed. The pH value was then 1.

Analytical results:

HCN 0 ppm formaldehyde cyanohydrin 74 ppm morpholinoacetonitrile 55 ppm

(Molar ratio HCN:CH₂O:morpholine=1:1.01:1.02; molar ratio morpholine:dimethylsulfate=1:1.21)

EXAMPLE 2

527.2 g (6.05 moles) of morpholine were introduced into the reaction vessel and cooled to 10° C. 6.6 g of aqueous caustic soda (20% by weight) were added in order to raise the pH value. Within a period of one hour, 600 g (6.0 moles) of formaldehyde (30% by weight) were then metered in. The addition of 161.6 g (5.94 moles) of hydrogen cyanide (99.25% by weight) started half an hour after the start of the addition of formaldehyde. The time of addition amounted to 1 hour. During the addition, the temperature was allowed to rise to 35° C. and stirring then took place for a further hour at 35° C. The pH value amounted to 11.4 at the end of this part of the synthesis. The pH was then adjusted to 8-8.2 with sulfuric acid. Cooling to 30° C. then took place and 932.4 g (7.4 moles) of dimethylsulfate (DMS) were added within 2 hours at 30° C. During the DMS addition, the pH value fell into the acidic region starting from 8. At pH 3.5, the pH-regulated addition of aqueous caustic soda (25% by weight) was counter-controlled so that the pH remained constant at 3.5 during the remaining addition time and the following post-reaction time of 3 hour at 30° C. The mixture was then heated to 50° C. and the pH value was allowed to fall in this connection. After 1 hour at 50° C., the excess DMS was completely destroyed. The pH value was then 1.

Analytical results:

HCN 0 ppm formaldehyde cyanohydrin 10 ppm morpholinoacetonitrile 20 ppm

(Molar ratio HCN:CH₂O:morpholine=1:1.01:1.02; molar ratio morpholine:dimethylsulfate=1:1.22)

EXAMPLE 3

537.2 g (6.17 moles) of morpholine were introduced into the reaction vessel and cooled to 10° C. 6.7 g of aqueous caustic soda (20% by weight) were added in order to raise the pH value. Within a period of one hour, 600 g (6.0 moles) of formaldehyde (30% by weight) were then metered in. The addition of 161.6 g (5.94 moles) of hydrogen cyanide (99.25% by weight) started half an hour after the start of the addition of formaldehyde. The time of addition amounted to 1 hour. During the addition, the temperature was allowed to rise to 35° C. and stirring then took place for a further hour at 35° C. The pH value amounted to 11.8 at the end of this part of the synthesis. The pH was then adjusted to 8-8.2 with sulfuric acid. Cooling to 30° C. then took place and 940 g (7.46 moles) of dimethylsulfate (DMS) were added at 30° C. within 2 hours. During the DMS addition, the pH value fell into the acidic region starting from 8. At pH 3.5, the pH-regulated addition of aqueous caustic soda (25% by weight) was counter-controlled so that the pH remained constant at 3.5 during the remaining addition time and the following post-reaction time of 3 hour at 30° C. The addition of caustic soda took place with good mixing (stirring conditions of 800 revolutions/minute). The mixture was then heated to 50° C. and the pH value was allowed to fall in this connection. After 1 hour at 50° C., the excess DMS was completely destroyed. The pH value was then 1.

Analytical results:

HCN 0 ppm formaldehyde cyanohydrin 0 ppm morpholinoacetonitrile 20 ppm N-methylmorpholinium 58.0% by wt. acetonitrile methylsulfate N-methylmorpholinium 3.0% by wt. acetamide methylsulfate

(Molar ratio HCN:CH₂O:morpholine=1:1.01:1.04; molar ratio morpholine:dimethylsulfate=1:1.21)

Example 4 illustrates another aspect of the invention, which is the preparation of substantially solid bisulfate salts, such as to prepare MMABS.

EXAMPLE 4

The methylsulfate liquid, such as in any of Examples 1-3, was acidified to a pH of 0.1-1 followed by heating the resulting liquid under a slight vacuum (700-1000 mbar) in a vented container at temperatures of 90-110° C. for 3-5 hours.

The resulting bisulfate converted liquid may then be crystallized and purified for recovery of crystalline nitrile salt, may be dried directly onto a support/carrier to produce an amorphous salt, or may be redissolved after crystallization and then prepared in granule form. One preferred approach to promote the crystallization or precipitation may be via addition of a “seed crystal,” which serves as a growth location for crystal formation. This seed crystal can be, but is not limited to, precipitated or fumed silica, or a sample of the bisulfate crystal salt itself. Another preferred approach is to allow the salt solution to precipitate out by reducing the crystal solubility via cooling over time.

EXAMPLE 5

96 kg of MMAMS liquid (48.5% active) were acidified with 6.7 kg of sulfuric acid (50%) at 20° C. and subsequently heated to 110° C. for 4½ hours after which the solution was cooled to 30° C. over an 18 hour period. The resulting slurry was then washed with water and filtered to yield the resulting bisulfate crystal (61.7 kg).

When one wishes to prepare the nitrile salts in granule form, such can be by use of various methods known to the art, such as fluid bed, agglomerating, spray coating, or melt mixing approaches, preferably at levels of about 5-40 wt. % of the starting particulate weight. These granules may have the nitrile salts carried on solid particulate or may have the nitrile salt coated by or admixed with solid particulate.

Conditions for coating preferably are whereby the temperature during coating is less than about 50° C. while the coating material is sprayed as a melt or dispersion onto the salt surface thereby coating or encapsulating the salt core. Example 6 illustrates different forms of the salt core and a variety of preferred coating materials. Anticipated coating materials include film-forming polymers, fatty acids, soaps, and other solid surfactants having a melting point above 40° C.

EXAMPLE 6

Nitrile Salt Core Preferred Coatings Materials Purified crystal salt PLURONIC 6800¹ Amorphous compacted salt PLURONIC 10500¹ Amorphous agglomerated salt PLURIOL E 6000¹ Amorphous acidified salt SOKALAN CP5¹ LUWAX V¹ Polyvinyl alcohol Palmitic acid Paraffin Calcium Alginate POLIGEN WE3¹ DIOFAN 193D¹ ¹Commercially available from BASF AG, Germany.

Particularly preferred coating materials are PLURIOL E6000 and LUWAX V. (PLURONIC is a trademark for a series of poly(oxyethylene-co-oxypropylene) block copolymers.)

EXAMPLE 7

Preparation of a solid MMAMS/silicic acid/surfactant composition using a stirring process

3.4 kg of a highly dispersed silicic acid with a total surface area of approximately 450 m²/g and an average particle size of approximately 8 mm (SIPERNAT® 50 S from the Degussa firm) and, additionally, 2.3 kg of a tallow-based fatty alcohol that had been reacted with 25 mol of ethylene oxide (Lutensol® AT 25 from the BASF firm) were stirred into 24.3 kg of a 70% by weight aqueous solution of N-methylmorpholinium acetonitrile methylsulfate (MMAMS). The liquid mixture was concentrated by evaporation in a paddle-type vacuum dryer at approximately 10 mbar and a wall temperature of approximately 80° C. until a solid was formed that was capable of flowing (residual water content <1% by weight). After cooling, 20 kg of the solid composition were removed. The powder was compacted by means of a conventional compactor to give flakes and the flakes were then broken up in a conventional sieve granulator and sieved to give a usable fraction of 400 to 1200 mm average size.

EXAMPLE 8

Manufacture of a solid MMAMS/silicic acid/surfactant composition by means of a spray process

24.3 kg of a 70% by weight MMAMS solution were sprayed onto 31.6 kg of the highly dispersed silicic acid that was described in Example 7. The crumbly mixture was dried in a paddle-type vacuum dryer at approximately 10 mbar and a wall temperature of approximately 80° C. until a fine solid was formed that was capable of flowing (residual water content <1% by weight). The product was then agglomerated in a mixture with a melt of 2.3 kg of the surfactant that was designated in Example 7. Final processing to give a usable fraction of 400 to 1200 mm was carried out analogously to Example 7.

EXAMPLE 9

Effect of carrier materials and surfactants on the hygroscopic characteristics or, as the case may be, the flow characteristics of MMAMS

In order to ascertain the effect of ancillary substances on the hygroscopic characteristics or, as the case may be, the flow characteristics of MMAMS, three different samples were prepared in the paddle-type dryer and were then stored in a desiccator at room temperature and a relative atmospheric humidity of 76%.

Sample 1: 2100 g MMAMS (solid) Sample 2: 3100 g MMAMS (solid) 400 g SIPERNAT 50 S Sample 3: 3100 g MMAMS (solid) 400 g SIPERNAT 50 S 233g Lutensol AT 25

All the samples were prepared from a 70% by weight aqueous MMAMS solution analogously to Example 7 and were dried at 80° C. and 10 mbar in a paddle-type vacuum dryer with a volume of 5 liters until no more condensate was generated.

In the case of Examples 8 and 9, one obtained a powder-type solid, that was capable of flowing after drying, with water contents of 0.74% by weight or 0.45% by weight, respectively; the MMAMS without the ancillary substances (sample 1) led to a wax-like, crumbly solid with a water content of 0.63% by weight.

These solids were then ground to the same average particle size and were stored in the desiccator. The results are presented in the following Table 2.

It is clearly seen that solid MMAMS is obtained in a high concentration and is stable on storage over a long period of time at a relative atmospheric humidity of 76% only as a result of the addition of the designated ancillary substances.

TABLE 2 Storage time 0 hr 17 hrs 41 hrs 113 hrs Water Content % 0.63 5.23 9.23 9.8 Sample 1 Ability to Flow capable of baked on partially partially Sample 1 flowing detached detached Water Content % 0.74 5.04 9.04 11.44 Sample 2 Ability to Flow capable of capable of small clumps slightly baked Sample 2 flowing flowing on Water Content % 0.45 3.65 6.15 8.55 Sample 3 Ability to Flow capable of capable of capable of capable of Sample 3 flowing flowing flowing flowing

EXAMPLE 10

Effect of carrier materials on the storage stability and dye damage characteristics

Samples of MMAMS on various carriers were prepared and put in a bleaching composition to determine any benefit in storage stability or dye damage.

Storage Stability

The MMA methylsulfate has greater storage stability on an inert support, such as zeolite or clay. The presence of an acid sink, such as HLAS (alkylbenzenesulfonic acid), also enhances stability.

The MMA methylsulfate aqueous solution (3.6 g of 45%) was added to 38.5 g of sodium carbonate containing 5.0 g of sodium perborate monohydrate and the solid dried. This was compared to first adding the MMA methylsulfate to 6 parts of zeolite 4A (Valfour 100 from PQ Corp.) and then adding to the sodium carbonate/perborate mixture. The MMA methylsulfate could also be mixed with 6 parts of clay (Attapulgite L96117 from Oil-Dry Corp.) and then added to the sodium carbonate/perborate mixture. The MMA methylsulfate was also mixed with 2 parts of the same clay.

The results below in Table 3 show the surprisingly enhanced stability when the MMA methylsulfate is incorporated into the inventive supports.

TABLE 3 % MMA Active after MMA substrate in 1 wk Storage at Carbonate/Perborate 80° F./80% RH MAMS 0% MMAMS/Zeolite = 1/6 98% MMAMS/HLAS/Zeolite = 1/2/6 100% MMAMS/Clay = 1/6 100% MMAMS/Clay = 1/2 100%

Dye Damage Testing

The amount of MMAMS representing 5% of the base (sodium carbonate/perborate mixture) was placed on a diagnostic fabric (Brown 100% cotton dyed with Fast Orange RD, Direct Brown 5R and Rapideger Red LD). The MMAMS was covered with the base and then 10 ml of deionized water was applied. After 10 minutes, the fabric was rinsed and allowed to dry. The dye damage was visually evaluated on a 0 to 10 scale, where 0 represents no visible damage. The same samples as prepared above for the stability testing were used. The results again show the benefit of adding MMAMS to an inert support, with or without an acidic co-agent.

Nitrile Substrate Dye Damage Aqueous MMA methylsulfate 10 MMAMS/Zeolite = 1/6 3 MMAMS/HLAS/Zeolite = 1/2/6 1 MMAMS/Clay = 1/6 1

EXAMPLE 11

Continuous Conversion of MMA-MS Liquid to MMA-BS Solid and Subsequent Granulation

In order to obtain high content (at least 50%) nitrile active in the granules, different solid supports were chosen than in the above examples. For instance, the granules which contained zeolite were limited in the upper level of active they could carry. Additionally, it appeared that zeolite supports were sensitive to the low pHs resulting from the use of the preferred acid sinks, namely, sulfuric acid and sodium hydrogen sulfate (bisulfate). Thus, a silica support was used and was loaded with the preferred MMA-Bisulfate (“MMA-BS”) solution.

About 60 liters of a 65% by weight MMA-Methylsulfate (“MMA-MS”) solution were introduced into a glass reactor. The solution was heated to above 100° C. and kept at this temperature for 3 hours for evaporation under 50-600 mbar pressure. This resulted in a melt with an MMA-BS content of about 80%.

The melt was solidified in a Lödige mixer (Schugi, Bepex, O'Brien, Littleford, Eirich, fluid bed, paddle mixers, and other apparatuses may be utilized) with 20 kg of a commercial silica (e.g., such as Zeofree, from Huber Chemical; but Sipernat, Cab-O-Sil, Zeothix, Aerosil, Satintone and sodium sulfate are all other potentially suitable materials). The solidified mixture was screened, particles between the sizes of 350 and 1600 μm retained. Overs (that is, particles larger than 1600 μm) were ground and rescreened.

The MMA-BS content of the granules made with the above mentioned process was approximately 60%.

EXAMPLE 12

An especially preferred granule formulation is disclosed:

Ingredient Wt. % N-methylmorpholinium acetonitrile bisulfate 50%¹ 37% Precipitated Silica Support² NaHSO₄ (Stabilizing/Acidifying Agent) 0.5% Other (inerts, residual moisture) 12.5% 100.0% ¹Granules made by the preferred process had ˜65% content of MMA-BS ²Huber Chemicals

Analytical tests for chemical stability demonstrated that these granules retained high levels of the nitrile active over a 12 week period at 21.1° C. (75° F.), 26.7° C. (80° F.)/80% relative humidity, and 38° C. (100° F.).

It is to be understood that while the invention has been described above in conjunction with preferred specific embodiments, the description and examples are intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. 

It is claimed:
 1. Granules, useful for oxidizing applications when dissolved in the presence of an active oxygen source, comprising: a salt having the structure of Formula I

 wherein A is a saturated ring formed by a plurality of atoms in addition to the N₁ atom, the saturated ring atoms including at least one carbon atom and at least one heteroatom in addition to the N₁ atom, the said heteroatom selected from the group consisting of O, S and N atoms, the substituent R₁ bound to the N₁ atom of the Formula I structure is (a) a C₁₋₈ alkyl or alkoxylated alkyl where the alkoxy is C₂₋₄, (b) a C₄₋₂₄ cycloalkyl, (c) a C₇₋₂₄ alkylaryl, (d) a repeating or nonrepeating alkoxy or alkoxylated alcohol, where the alkoxy unit is C₂₋₄, or (e) CR₂, R₃, CN, where R₂, and R₃, are each H, a C₁₋₂₄ alkyl, cycloalkyl, or alkylaryl, or a repeating or nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit is C₂₋₄, the R₂ and R₃ substituents are each H, a C₁₋₂₄ alkyl, cycloalkyl, or alkylaryl, or a repeating or nonrepeating alkoxyl or alkoxylated alcohol where the alkoxy unit is C₂₋₄, and wherein Y is an counterion and Z is in the range of 0 to 10, and wherein Y is a counterion.
 2. The granules as in claim 1 wherein A of Formula I is a saturated ring formed by four carbon atoms and one oxygen atom in addition to the N₁ atom.
 3. The granules as in claim 1 wherein A of Formula I is a saturated ring formed by four carbon atoms and an N₂ atom in addition to the N₁ atom, with N₂ being a secondary amine, a tertiary amine having the substituent —CR₅R₆CN or a quaternary amine having the substituents —R₅ and —CR₅R₆CN, wherein R₅ and R₆ are individually H or C₁₋₆ alkyl.
 4. The granules as in claim 1 wherein the support is in an amount of about 2 to about 95 parts by weight of the granules and has a total surface area of 10 to 500 m²/g.
 5. The granules as in claim 1 wherein the support is a silica gel, silicic acid, silicate, aluminum oxide, clay, alkali metal sulfate or mixtures thereof.
 6. The granules as in claim 1 further comprising a coating sufficient to delay dissolution in aqueous solution.
 7. The granules as in claim 1 further comprising an acidic agent.
 8. The granules as in claim 1 having a water content, including water of hydration, of less than about 20 wt. %.
 9. The granules as in claim 1 wherein the counterion is sulfate, bisulfate, methylsulfate, or tosylate.
 10. The granules as in claim 1 wherein Z of the salt is 0 to
 6. 11. The granules as in claim 1 having from about 1 to about 99 wt. % of the Formula I salt therein.
 12. The granules as in claim 1 having an average particle size of about 3 nm to about 2 mm.
 13. The granules as in claim 1 including a surfactant or a mixture of surfactants in an amount of about 0.5 to about 50 parts by weight.
 14. The granules as in claim 1 wherein R₁ is methyl.
 15. The granules as in claim 14 wherein R₂ and R₃ are both hydrogen.
 16. The granules as in claim 1 wherein the formula I salt has a content of at least 50%.
 17. The granules as in claim 16 wherein the formula I salt has a content of at least 60%.
 18. A bleaching composition, comprising: the granules as in claim 1; and a source of active oxygen.
 19. The bleaching composition as in claim 18 further including an alkaline buffer.
 20. The bleaching composition as in claim 18 further including a chelating agent.
 21. The bleaching composition as in claim 18 further including one or more of a brightening agent and a whitening agent.
 22. The bleaching composition as in claim 18 further including an enzyme.
 23. The bleaching composition as in claim 18 wherein from about 1 to about 70 percent active peroxyimidic acid derivative is provided on the basis of the bleaching composition weight when dissolved in an alkaline solution. 